CN105481253B - A kind of preparation method of compound low temperature sealing glass solder soldering paste - Google Patents
A kind of preparation method of compound low temperature sealing glass solder soldering paste Download PDFInfo
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- CN105481253B CN105481253B CN201510907136.5A CN201510907136A CN105481253B CN 105481253 B CN105481253 B CN 105481253B CN 201510907136 A CN201510907136 A CN 201510907136A CN 105481253 B CN105481253 B CN 105481253B
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- glass powder
- soldering paste
- powder
- whisker
- low temperature
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
Abstract
A kind of preparation method of compound low temperature sealing glass solder soldering paste, it is related to a kind of preparation method of solder soldering paste.It will solve that existing low temperature sealing glass solder thermal expansion coefficient adjustable extent is small and the problem of soldered fitting performance difference.Method: one, parent glass powder is classified；Two, raw material is weighed；Three, β-Si3N4Whisker pretreatment；Four, silicon powder pre-processes；Five, mixing and ball milling；Six, it is mixed.The present invention is by adjusting β-Si in compound low temperature sealing glass solder soldering paste3N4The additive amount of whisker and/or silicon powder, i.e., the thermal expansion coefficient of controllable low temperature sealing glass, method is simple, at low cost；Soldering joint strength, thermal shock resistance and the toughness of acquisition are all significantly improved, and have huge engineering application value.Compound low temperature sealing glass solder soldering paste prepared by the present invention is suitable for the interconnection between ceramics, metal, glass and composite material and connects certainly, widely used.
Description
Technical field
The present invention relates to a kind of preparation methods of solder soldering paste.
Background technique
Low temperature sealing glass refers to the middle layer glass for sealing up glass, ceramics, metal and composite material etc. each other
Glass.Due to lower glass melting temperature and sealing temperature, good chemical stability and heat resistance and higher mechanical strength,
The mutual sealing-in being commonly used between glass, ceramics, metal and composite material, in electrovacuum and microelectric technique, laser and red
The various fields such as outer technology, high-energy physics, the energy, aerospace, automobile, chemical industry and industrial test are widely used.
Glass has certain limitation as a kind of seal, sealing materials: first is that thermal expansion coefficient is difficult to adjust and adjustable model
It encloses small, currently mainly realizes the adjusting of thermal expansion coefficient by adjusting glass ingredient, the different base material of sealing-in needs to prepare phase
The glass solder of ingredient is answered, at high cost and process is complicated；Second is that the brittleness of glass itself is bigger, the soldering joint strength of formation
It is poor with thermal shock resistance, especially base material difference of thermal expansion coefficients is larger or base material and glass for sealing thermal expansion coefficient it is inconsistent
When, the stress of generation can be such that joint cracks, and seriously affect the intensity and air-tightness of connector.
Summary of the invention
It is small the invention aims to solve existing low temperature sealing glass solder thermal expansion coefficient adjustable extent, and soldering
The problem of joint performance difference, and a kind of preparation method of compound low temperature sealing glass solder soldering paste is provided.
The preparation method of compound low temperature sealing glass solder soldering paste, sequentially includes the following steps:
One, parent glass powder is classified: parent glass powder being placed in ball grinder, by abrading-ball and parent glass powder quality
Than for (30~60): abrading-ball is added in 1 ratio, with revolving speed 2~6h of dry ball milling of 200~300r/min, divides after taking out powder
200 mesh, 400 mesh and 500 meshes, the parent glass powder after being screened are not crossed；
Two, it weighs: parent glass powder and A substance after weighing screening respectively；Wherein A substance is β-Si3N4Whisker, silicon powder
One of or two kinds of mixing, β-Si3N4The mass ratio of whisker and parent glass powder is (0.2~6): (94~99.8), silicon powder
Mass ratio with parent glass powder is (0.1~0.2): (99.8~99.9), β-Si3N4The matter of whisker, silicon powder and parent glass powder
Amount is than being 0.2:0.2:99.6；
Three, β-Si3N4Whisker pretreatment: a, by weighed β-Si3N4Whisker is placed in dehydrated alcohol, at room temperature
Filtration drying after 2~3h of magnetic agitation；B, by the β-Si by step a processing3N4Whisker is placed in heating furnace, with 10~15 DEG C/
The rate of heat addition of min is heated to 1000~1100 DEG C, furnace cooling after 2~4h is kept the temperature, during which to heating furnace with 100Nm3/ h~
250Nm3The throughput of/h is passed through oxygen；C, by the β-Si by step b processing3N4Whisker repeats operation 1 time of step a；
Four, silicon powder pre-processes: a, silicon powder being placed in dehydrated alcohol, is filtered after 2~3h of magnetic agitation at room temperature
It is dry；B, will by step a processing silicon powder be added in mixed acid solution, under the conditions of 50~70 DEG C magnetic agitation 30~
50min, being cooled to after room temperature in air and being washed with distilled water to pH value is 7；C, it will repeat to walk by the silicon powder of step b processing
Operation 1 time of rapid a；
Five, pretreated β-Si mixing and ball milling: will be passed through3N4Whisker or silicon powder, parent glass powder and dehydrated alcohol are together
It is put into ball grinder, then under the protection of nitrogen atmosphere, with revolving speed 1~4h of ball milling of 200~300r/min, obtains compound
Low meiting sealing frils；
Six, it is mixed: terpinol and dehydrated alcohol 10:(1~10 by volume) it is configured to binder, be in revolving speed
Under 100~150r/min, compound low meiting sealing frils and bonding agent are placed in 0.5~2h of stirring in soldering paste blender, are obtained
To compound low temperature sealing glass solder soldering paste；
Wherein parent glass powder described in step 1 is bismuthates lead-free low-temperature seal glass powder, phosphate-based unleaded
Low meiting sealing frils body or borate-based lead-free low-temperature seal glass powder；
The bismuthates system lead-free low-temperature seal glass powder, by mass fraction by 50~60 parts of Bi2O3, 20~30 parts
B2O3, 5~15 parts of BaO, 2~10 parts of ZnO, 0.1~1 part of A12O3, 0.1~1 part of SiO2With 0.1~1 part of Li2O composition；
The phosphate-based lead-free low-temperature seal glass powder, by mass fraction by 40~60 parts of P2O5, 10~20 parts
SnO, 10~20 parts of ZnO, 5~10 parts of B2O3, 0.1~3 part of A12O3, 0.1 part~3 parts of SiO2With 0.1~1 part of Li2O composition；
The borate-based lead-free low-temperature seal glass powder, by mass fraction by 50~70 parts of B2O3, 10~20 parts
P2O5, 10~20 parts of ZnO, 0.1~1 part of A12O3, 0.1~1 part of SiO2With 0.1~1 part of Li2O composition.
Advantages of the present invention is as follows: by adjusting β-Si in compound low temperature sealing glass solder soldering paste3N4Whisker and/or
The additive amount of silicon powder, i.e., the thermal expansion coefficient of controllable low temperature sealing glass, method is simple, at low cost；The soldered fitting of acquisition
Intensity, thermal shock resistance and toughness are all significantly improved, and have huge engineering application value.It is made using the above method
Compound low temperature sealing glass solder soldering paste thermal expansion coefficient 80~135 × 10-7/ DEG C between be continuously adjusted, sealing-in temperature
Degree is 400~610 DEG C, and the room temperature shear strength of the Welding part of acquisition improves about 30~55%.It is prepared by the present invention compound
Type low temperature sealing glass solder soldering paste is suitable for the interconnection between ceramics, metal, glass and composite material and connects certainly, and purposes is wide
It is general.
Specific embodiment
Specific embodiment 1: the preparation method of the compound low temperature sealing glass solder soldering paste of present embodiment, by following
Step carries out:
One, parent glass powder is classified: parent glass powder being placed in ball grinder, by abrading-ball and parent glass powder quality
Than for (30~60): abrading-ball is added in 1 ratio, with revolving speed 2~6h of dry ball milling of 200~300r/min, divides after taking out powder
200 mesh, 400 mesh and 500 meshes, the parent glass powder after being screened are not crossed；
Two, it weighs: parent glass powder and A substance after weighing screening respectively；Wherein A substance is β-Si3N4Whisker, silicon powder
One of or two kinds of mixing, β-Si3N4The mass ratio of whisker and parent glass powder is (0.2~6): (94~99.8), silicon powder
Mass ratio with parent glass powder is (0.1~0.2): (99.8~99.9), β-Si3N4The matter of whisker, silicon powder and parent glass powder
Amount is than being 0.2:0.2:99.6；
Three, β-Si3N4Whisker pretreatment: a, by weighed β-Si3N4Whisker is placed in dehydrated alcohol, at room temperature
Filtration drying after 2~3h of magnetic agitation；B, by the β-Si by step a processing3N4Whisker is placed in heating furnace, with 10~15 DEG C/
The rate of heat addition of min is heated to 1000~1100 DEG C, furnace cooling after 2~4h is kept the temperature, during which to heating furnace with 100Nm3/ h~
250Nm3The throughput of/h is passed through oxygen；C, by the β-Si by step b processing3N4Whisker repeats operation 1 time of step a；
Four, silicon powder pre-processes: a, silicon powder being placed in dehydrated alcohol, is filtered after 2~3h of magnetic agitation at room temperature
It is dry；B, will by step a processing silicon powder be added in mixed acid solution, under the conditions of 50~70 DEG C magnetic agitation 30~
50min, being cooled to after room temperature in air and being washed with distilled water to pH value is 7；C, it will repeat to walk by the silicon powder of step b processing
Operation 1 time of rapid a；
Five, pretreated β-Si mixing and ball milling: will be passed through3N4Whisker or silicon powder, parent glass powder and dehydrated alcohol are together
It is put into ball grinder, then under the protection of nitrogen atmosphere, with revolving speed 1~4h of ball milling of 200~300r/min, obtains compound
Low meiting sealing frils；
Six, it is mixed: terpinol and dehydrated alcohol 10:(1~10 by volume) it is configured to binder, be in revolving speed
Under 100~150r/min, compound low meiting sealing frils and bonding agent are placed in 0.5~2h of stirring in soldering paste blender, are obtained
To compound low temperature sealing glass solder soldering paste；
Wherein parent glass powder described in step 1 is bismuthates lead-free low-temperature seal glass powder, phosphate-based unleaded
Low meiting sealing frils body or borate-based lead-free low-temperature seal glass powder；
The bismuthates system lead-free low-temperature seal glass powder, by mass fraction by 50~60 parts of Bi2O3, 20~30 parts
B2O3, 5~15 parts of BaO, 2~10 parts of ZnO, 0.1~1 part of A12O3, 0.1~1 part of SiO2With 0.1~1 part of Li2O composition；
The phosphate-based lead-free low-temperature seal glass powder, by mass fraction by 40~60 parts of P2O5, 10~20 parts
SnO, 10~20 parts of ZnO, 5~10 parts of B2O3, 0.1~3 part of A12O3, 0.1 part~3 parts of SiO2With 0.1~1 part of Li2O composition；
The borate-based lead-free low-temperature seal glass powder, by mass fraction by 50~70 parts of B2O3, 10~20 parts
P2O5, 10~20 parts of ZnO, 0.1~1 part of A12O3, 0.1~1 part of SiO2With 0.1~1 part of Li2O composition.
The partial size of parent glass powder after screening in present embodiment step 1 is 20~70 μm.
The purpose that oxygen is passed through in present embodiment step 3 b is in β-Si3N4Whisker surface forms one layer of SiO2, to increase
Add the compatibility of itself and parent glass powder.
Binder described in present embodiment step 6 controls soldering paste viscosity, dehydrated alcohol amount by the amount of dehydrated alcohol
More, viscosity is smaller.
Specific embodiment 2: the present embodiment is different from the first embodiment in that, abrading-ball and base are pressed in step 1
Abrading-ball is added in the ratio that plinth glass powder mass ratio is 45:1, with the revolving speed dry ball milling 4h of 260r/min.Other and specific reality
It is identical to apply mode one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that, mill described in step 1
Ball is ZrO2Ceramic grinding ball.It is other the same as one or two specific embodiments.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three, β-in step 2
Si3N4The mass ratio of whisker and parent glass powder is 4.5:95.5.It is other identical as one of specific embodiment one to three.
Specific embodiment 5: step 2 is in silicon unlike one of present embodiment and specific embodiment one to four
The mass ratio of powder and parent glass powder is 0.15:99.85.It is other identical as one of specific embodiment one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five, described in step 2
β-Si3N4The diameter of whisker is 0.05~0.2 μm, draw ratio >=20,99% or more purity.Other and specific embodiment one
It is identical to one of five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six, described in step 2
Silicon powder average particle size be 30~50 μm.It is other identical as one of specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven, it will in step 3
β-the Si handled by step a3N4Whisker is placed in heating furnace, is heated to 1050 DEG C with the rate of heat addition of 12 DEG C/min, is kept the temperature 3h
Furnace cooling afterwards, during which to heating furnace with 150Nm3The throughput of/h is passed through oxygen.It is other with specific embodiment one to seven it
One is identical.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight, step 4 will be through
The silicon powder for crossing step a processing is added in mixed acid solution, magnetic agitation 40min under the conditions of 60 DEG C.Other and specific embodiment party
One of formula one to eight is identical.
Specific embodiment 10: being mixed in step 4 b unlike one of present embodiment and specific embodiment one to nine
Acid solution is the sulfuric acid of mass concentration 20%~25% and the hydrochloric acid of mass concentration 20%~25%, liquid-solid ratio sulfuric acid: hydrochloric acid: silicon
Powder is (2~2.5): (1.5~2): 1.It is other identical as one of specific embodiment one to nine.
Specific embodiment 11: unlike one of present embodiment and specific embodiment one to ten, in step 5
With the revolving speed ball milling 3h of 260r/min.It is other identical as one of specific embodiment one to ten.
Specific embodiment 12: present embodiment is unlike specific embodiment one to one of 11, step 5
It is middle to pass through pretreated β-Si3N4The ratio between whisker or silicon powder, the gross mass of parent glass powder and the volume of dehydrated alcohol are
100g:(350~450ml).It is other identical as specific embodiment one to one of 11.
Specific embodiment 13: present embodiment is unlike specific embodiment one to one of 12, step 5
In can also be will pass through pretreated β-Si3N4Whisker, silicon powder, parent glass powder and dehydrated alcohol are put into ball grinder together.
It is other identical as specific embodiment one to one of 12.
Specific embodiment 14: present embodiment is unlike specific embodiment 13, by pre- in step 5
β-the Si of processing3N4The ratio between volume of whisker, silicon powder, the gross mass of parent glass powder and dehydrated alcohol for 100g:(350~
450ml).It is other identical as specific embodiment 13.
Specific embodiment 15: present embodiment is unlike specific embodiment one to one of 14, step 6
10:5 is configured to binder to middle terpinol by volume with dehydrated alcohol, and in the case where revolving speed is 120r/min, compound low temperature is sealed
It connects glass powder and bonding agent is placed in soldering paste blender and stirs 1h.It is other identical as specific embodiment one to one of 14.
Specific embodiment 16: present embodiment is unlike specific embodiment one to one of 15, step 6
In the mass ratio of compound low meiting sealing frils and bonding agent be 1:(0.3~0.6).Other and specific embodiment one to ten
One of five is identical.
Beneficial effects of the present invention are verified by following embodiment:
Embodiment 1:
The preparation method of compound low temperature sealing glass solder soldering paste, sequentially includes the following steps:
One, parent glass powder is classified: parent glass powder being placed in ball grinder, by abrading-ball and parent glass powder quality
Than abrading-ball is added for the ratio of 50:1, with the revolving speed dry ball milling 3h of 300r/min, 200 mesh, 400 mesh are crossed respectively after taking out powder
With 500 meshes, parent glass powder after being screened；
Two, it weighs: weighing β-Si respectively3N4Parent glass powder after whisker and screening, wherein β-Si3N4Whisker and basis
The mass ratio of glass powder is 0.2:99.8；
Three, β-Si3N4Whisker pretreatment: a, by weighed β-Si3N4Whisker is placed in dehydrated alcohol, at room temperature
Filtration drying after magnetic agitation 2h；B, by the β-Si by step a processing3N4Whisker is placed in heating furnace, with adding for 15 DEG C/min
Hot rate is heated to 1000 DEG C, furnace cooling after 4h is kept the temperature, during which to heating furnace with 250Nm3The throughput of/h is passed through oxygen；c,
By the β-Si by step b processing3N4Whisker repeats operation 1 time of step a；
Four, pretreated β-Si mixing and ball milling: will be passed through3N4Whisker, parent glass powder and dehydrated alcohol are put into ball milling together
In tank, then under the protection of nitrogen atmosphere, with the revolving speed ball milling 2h of 300r/min, compound low meiting sealing frils are obtained；
Six, be mixed: 10:5 is configured to binder by volume for terpinol and dehydrated alcohol, is 120r/min in revolving speed
Under, compound low meiting sealing frils and bonding agent are placed in soldering paste blender and stir 1h, obtain compound low-temperature sealing glass
Glass solder soldering paste；
Wherein parent glass powder described in step 1 be bismuthates lead-free low-temperature seal glass powder, by mass fraction by
50~60 parts of Bi2O3, 20~30 parts of B2O3, 5~15 parts of BaO, 2~10 parts of ZnO, 0.1~1 part of A12O3, 0.1~1 part of SiO2With
0.1~1 part of Li2O composition.
The partial size of parent glass powder after screening in the present embodiment step 1 is 40 μm.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
82~101 × 10-7/ DEG C, sealing temperature is 420~550 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 33%, and thermal shock resistance improves.
Embodiment 2:
It is not both β-Si described in step 2 with embodiment 13N4The mass ratio of whisker and parent glass powder is 1.0:
99.0；It is other same as Example 1.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
87~109 × 10-7/ DEG C, sealing temperature is 430~570 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 35%, and thermal shock resistance improves.
Embodiment 3:
It is not both β-Si described in step 2 with embodiment 13N4The mass ratio of whisker and parent glass powder is 2.5:
97.5；It is other same as Example 1.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
91~112 × 10-7/ DEG C, sealing temperature is 460~570 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 39%, and thermal shock resistance improves.
Embodiment 4:
It is not both β-Si described in step 2 with embodiment 13N4The mass ratio of whisker and parent glass powder is 3:97；Its
It is same as Example 1.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
95~120 × 10-7/ DEG C, sealing temperature is 450~580 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 44%, and thermal shock resistance improves.
Embodiment 5:
It is not both β-Si described in step 2 with embodiment 13N4The mass ratio of whisker and parent glass powder is 4.5:
95.5；It is other same as Example 1.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
98~127 × 10-7/ DEG C, sealing temperature is 490~590 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 49%, and thermal shock resistance improves.
Embodiment 6:
It is not both β-Si described in step 2 with embodiment 13N4The mass ratio of whisker and parent glass powder is 6:94；Its
It is same as Example 1.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
102~131 × 10-7/ DEG C, sealing temperature is 500~600 DEG C, is connected using the compound low temperature bonding glass solder soldering paste
Test specimen, the shear strength of connector at room temperature improve 53%, and thermal shock resistance improves.
Embodiment 7:
The preparation method of compound low temperature sealing glass solder soldering paste, sequentially includes the following steps:
One, parent glass powder is classified: parent glass powder being placed in ball grinder, by abrading-ball and parent glass powder quality
Than abrading-ball is added for the ratio of 50:1, with the revolving speed dry ball milling 2h of 300r/min, 200 mesh, 400 mesh are crossed respectively after taking out powder
With 500 meshes, parent glass powder after being screened；
Two, it weighs: weighing silicon powder and the parent glass powder after screening respectively, wherein the mass ratio of silicon powder and parent glass powder
For 0.1:99.9；
Three, silicon powder pre-processes: a, silicon powder being placed in dehydrated alcohol, crosses be filtered dry after magnetic agitation 3h at room temperature
It is dry；B, it will be added in mixed acid solution by the silicon powder of step a processing, magnetic agitation 30min under the conditions of 70 DEG C, in air
Being cooled to after room temperature and being washed with distilled water to pH value is 7；C, it will be repeated operation 1 time of step a by the silicon powder of step b processing；
Four, pretreated β-Si mixing and ball milling: will be passed through3N4Whisker or silicon powder, parent glass powder and dehydrated alcohol are together
It is put into ball grinder, then under the protection of nitrogen atmosphere, with the revolving speed ball milling 1h of 300r/min, obtains compound low-temperature sealing
Glass powder；
Five, be mixed: 10:6 is configured to binder by volume for terpinol and dehydrated alcohol, is 150r/min in revolving speed
Under, compound low meiting sealing frils and bonding agent are placed in soldering paste blender and stir 1h, obtain compound low-temperature sealing glass
Glass solder soldering paste；
Wherein parent glass powder described in step 1 is phosphate-based lead-free low-temperature seal glass powder, by mass fraction
By 40~60 parts of P2O5, 10~20 parts of SnO, 10~20 parts of ZnO, 5~10 parts of B2O3, 0.1~3 part of A12O3, 0.1 part~3 parts of SiO2
With 0.1~1 part of Li2O composition.
The partial size of parent glass powder after screening in the present embodiment step 1 is 50 μm.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
83~110 × 10-7/ DEG C, sealing temperature is 430~580 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 35%, and thermal shock resistance improves.
Embodiment 8:
It is not both the mass ratio of silicon powder described in step 2 and parent glass powder is 0.15:99.85 with embodiment 7；Its
It is same as Example 7.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
89~118 × 10-7/ DEG C, sealing temperature is 470~590 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 41%, and thermal shock resistance improves.
Embodiment 9:
It is not both the mass ratio of silicon powder described in step 2 and parent glass powder is 0.2:99.8 with embodiment 7；It is other
It is same as Example 7.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
95~127 × 10-7/ DEG C, sealing temperature is 510~600 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 50%, and thermal shock resistance improves.
Embodiment 10:
It is not both β-Si is also weighed in step 2 with embodiment 73N4Whisker, and using method pair in 1 step 3 of embodiment
β-Si3N4Whisker is pre-processed；β-Si3N4The mass ratio of whisker, silicon powder and parent glass powder is 0.2:0.2:99.6；It is other
It is same as Example 7.
The present embodiment prepares resulting compound low temperature bonding glass solder soldering paste, and by test, thermal expansion coefficient is
86~121 × 10-7/ DEG C, sealing temperature is 420~850 DEG C, the examination connected using the compound low temperature bonding glass solder soldering paste
Part, the shear strength of connector at room temperature improve 43%, and thermal shock resistance improves.
Claims (5)
1. a kind of preparation method of compound low temperature sealing glass solder soldering paste, it is characterised in that it is sequentially included the following steps:
One, parent glass powder is classified: parent glass powder being placed in ball grinder, is by abrading-ball and parent glass powder quality ratio
(30~60): abrading-ball is added in 1 ratio, with revolving speed 2~6h of dry ball milling of 200~300r/min, takes out after powder mistake respectively
200 mesh, 400 mesh and 500 meshes, the parent glass powder after being screened；
Two, it weighs: parent glass powder and A substance after weighing screening respectively；Wherein A substance is β-Si3N4Whisker and silicon powder it is mixed
It closes, β-Si3N4The mass ratio of whisker, silicon powder and parent glass powder is 0.2:0.2:99.6；
Three, β-Si3N4Whisker pretreatment: a, by weighed β-Si3N4Whisker is placed in dehydrated alcohol, and magnetic force stirs at room temperature
Mix filtration drying after 2~3h；B, by the β-Si by step a processing3N4Whisker is placed in heating furnace, with 10~15 DEG C/min's
The rate of heat addition is heated to 1000~1100 DEG C, furnace cooling after 2~4h is kept the temperature, during which to heating furnace with 100Nm3/ h~250Nm3/
The throughput of h is passed through oxygen；C, by the β-Si by step b processing3N4Whisker repeats operation 1 time of step a；
Four, silicon powder pre-processes: a, silicon powder being placed in dehydrated alcohol, at room temperature filtration drying after 2~3h of magnetic agitation；
B, it will be added in mixed acid solution by the silicon powder of step a processing, 30~50min of magnetic agitation under the conditions of 50~70 DEG C,
Being cooled to after room temperature in air and being washed with distilled water to pH value is 7；C, the behaviour of step a will be repeated by the silicon powder of step b processing
Make 1 time；
Five, pretreated β-Si mixing and ball milling: will be passed through3N4Whisker, silicon powder, parent glass powder and dehydrated alcohol are put into ball together
In grinding jar, then under the protection of nitrogen atmosphere, with revolving speed 1~4h of ball milling of 200~300r/min, compound low temperature envelope is obtained
Connect glass powder；
Six, be mixed: terpinol and dehydrated alcohol 10:(1~10 by volume) be configured to binder, revolving speed for 100~
Under 150r/min, compound low meiting sealing frils and bonding agent are placed in 0.5~2h of stirring in soldering paste blender, are obtained compound
Type low temperature sealing glass solder soldering paste；
Wherein parent glass powder described in step 1 is bismuthates system lead-free low-temperature seal glass powder, phosphate-based unleaded low
Intermediate temperature sealing glass powder or borate-based lead-free low-temperature seal glass powder；
The bismuthates system lead-free low-temperature seal glass powder, by mass fraction by 50~60 parts of Bi2O3, 20~30 parts of B2O3、5
~15 parts of BaO, 2~10 parts of ZnO, 0.1~1 part of A12O3, 0.1~1 part of SiO2With 0.1~1 part of Li2O composition；
The phosphate-based lead-free low-temperature seal glass powder, by mass fraction by 40~60 parts of P2O5, 10~20 parts of SnO, 10
~20 parts of ZnO, 5~10 parts of B2O3, 0.1~3 part of A12O3, 0.1 part~3 parts of SiO2With 0.1~1 part of Li2O composition；
The borate-based lead-free low-temperature seal glass powder, by mass fraction by 50~70 parts of B2O3, 10~20 parts of P2O5、10
~20 parts of ZnO, 0.1~1 part of A12O3, 0.1~1 part of SiO2With 0.1~1 part of Li2O composition；
β-Si described in step 23N4The diameter of whisker is 0.05~0.2 μm, draw ratio >=20,99% or more purity；Described
Silicon powder average particle size is 30~50 μm；
Mixed acid solution is the sulfuric acid of mass concentration 20%~25% and the hydrochloric acid of mass concentration 20%~25%, liquid in step 4 b
Gu than sulfuric acid: hydrochloric acid: silicon powder is (2~2.5): (1.5~2): 1.
2. a kind of preparation method of compound low temperature sealing glass solder soldering paste according to claim 1, pressed in step 1
Abrading-ball and parent glass powder quality are than being added abrading-ball for the ratio of 45:1, with the revolving speed dry ball milling 4h of 260r/min.
3. a kind of preparation method of compound low temperature sealing glass solder soldering paste according to claim 1, it is characterised in that
Abrading-ball described in step 1 is ZrO2Ceramic grinding ball.
4. a kind of preparation method of compound low temperature sealing glass solder soldering paste according to claim 1, it is characterised in that
10:5 is configured to binder to terpinol by volume with dehydrated alcohol in step 6, will be compound in the case where revolving speed is 120r/min
Low meiting sealing frils and bonding agent, which are placed in soldering paste blender, stirs 1h.
5. a kind of preparation method of compound low temperature sealing glass solder soldering paste according to claim 1, it is characterised in that
The mass ratio of compound low meiting sealing frils and bonding agent is 1:(0.3~0.6 in step 6).
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| CN108423998B (en) * | 2018-05-31 | 2021-10-08 | 北京北旭电子材料有限公司 | Glass powder composition, glass sealing material, preparation method of glass sealing material and battery |
| CN109439273B (en) * | 2018-09-18 | 2021-03-19 | 暨南大学 | Organic silicon lead compound hot-pressing sealing material for solar heat pipe vacuum heat collecting pipe and use method |
| CN114538779A (en) * | 2022-02-10 | 2022-05-27 | 浙江氢邦科技有限公司 | Preparation method of SOFC (solid oxide Fuel cell) packaging glass powder, SOFC packaging glass powder and SOFC packaging glass |
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| CN103402941A (en) * | 2011-02-18 | 2013-11-20 | 肖特公开股份有限公司 | Glass, in particular glass solder or fusible glass |
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| CN103402941A (en) * | 2011-02-18 | 2013-11-20 | 肖特公开股份有限公司 | Glass, in particular glass solder or fusible glass |
| CN103894694A (en) * | 2014-04-17 | 2014-07-02 | 哈尔滨工业大学 | Method for connection between composite type green low-melting solder glass and silicon carbide reinforced aluminum matrix composites |
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